Polyolefins modified with unsaturated glycidyl compounds and polyacrylate compounds

ABSTRACT

IN THE PRESENCE OF AN ORGANIC PEROXIDE THE MELT FLOW MAY BE CONTROLLED BY INCLUDING IN THE REACTANTS A MODIFIER COMPRISING ACRYLIC OR METHACRYLIC ESTERS OF DIOLS OR TRIOLS. The reaction product is particularly suitable for being reinforced with filamentary material such as glass fibers or asbestos or as a coating on metallic surfaces.   In modified polyolefin compositions prepared by reacting an olefin polymer with a polymerizable compound generally defined by

United States Patent Schrage et al.

[451 Oct. 17, 1972 [72] Inventors: Albert Schrage, East Orange; PhilipD. Readio, Sparta, both of NJ.

[73] Assignee: Dart Industries Inc'., Los Angeles,

Calif.

[22] Filed: March 30, 1971 [21] Appl. No.: 129,629

[52] US. Cl ..260/836, 260/94.7 A, 260/827, 260/878 R [51] Int. Cl...C08g 45/04 [58] Field of Search ..260/836, 94.7 A; 117/100 C [56]References Cited UNITED STATES PATENTS 3,423,481 1/1969 Mizutani..260/836 3,179,485 4/1965 Kawasaki ..204/159.l7

3,322,661 5/1967 Yoshikawa ..204/l59.l7

FOREIGN PATENTS OR APPLICATIONS 1,038,726 8/1966 Great Britain...260/857 3,713,880 9/1962 Japan 4,218,327 9/1967 Japan 4,316,3927/1968 Japan 4,328,461 12/1968 Japan 4,473,345 3/1969 Japan OTHERPUBLICATIONS Chemical Abstracts V01. Page Year Chemical Abstracts 597722c 1963 Chemical Abstracts 68 22496x 1968 Chemical Abstracts 7058846s 1969 Chemical Abstracts 70 79086j 1969 Chemical Abstracts 7122877j 1969 Chemical Abstracts 71 22878k 1969 Chemical Abstracts 7122879m 1969 Chemical Abstracts 71 14138d 1969 Primary Examiner-PaulLieberman Attorney-Fred S. Valles and Richard A. Dannells, Jr.

[57] ABSTRACT In modified polyolefin compositions prepared by reactingan olefin polymer with a polymerizable compound generally defined byonpti mksumn in the presence of an organic peroxide the melt flow may becontrolled by including in the reactants a modifier comprising acrylicor methacrylic esters of diols or triols. The reaction product isparticularly suitable for being reinforced with filamentary materialsuch as glass fibers or asbestos or as a coating on metallic surfaces.

8 Claims, No Drawings 1 POLYOLEFINS MODIFIED WITH UNSATURATED GLYCIDYLCOMPOUNDS AND POLYACRYLATE COMPOUNDS While the resulting modifiedpolyolefin compositions exhibit adhesiveness characteristics which arefar superior to the unmodified polyolefins the melt flow of thecompositions is'undesirably high. As is well known, polymers havingundesirably high melt flow values also undergo a decrease in physicalproperties such as tensile strength, flexural strength and impactstrength.

This invention provides a solution to the problems of unduly high meltflow in these modified polyolefin compositions. Briefly, the inventioninvolves the use of certain acrylic esters of diols and triols asmodifiers in group having one to 20 carbon atoms;

Q-cm-o-Q-m-Q- group wherein R is a straight or branched chain alkyleneradical having one to 10 carbon atoms, oxygen, sulfur, amino,

whereiri R' is l-T or lower alkyl and R is lower alkyl;

a RXR group" wherein each R is a straight or branched chain loweralkylene, X is an amino group or an oxygen or sulfur atom, and p is aninteger of one to 20;

the reaction of the olefin polymer with the ethylenically unsaturatedpolymerizable compound in the presence of the organic peroxide. Theseesters are merely charged along with the other reactants to a reactorand the entire mixture is subjected to the usual polymerizationconditions, The resulting modified polyolefin compositions have farlower melt flow values than such compositions prepared without the useof the modifiers.

The improved modified polyolefin compositions to which this inventionrelates are those derived by reacting an olefin polymer, 0.01 to 10percent by weight based on the olefin polymer of a polymerizablecompound defined by R CHz= -R Si(R); 1H

wherein R, R R R, and R are hereinafter defined, and 0.01 to percent byweight based on the olefin polymer of a modifier comprising acrylicesters of diols or triols in the presence of an organic peroxide.

The olefin polymer is one which is derived from alpha-olefin monomershaving two to 10 carbon atoms. Included among these are polyethylene,polypropylene, poly(butene-l), poly(4-methyl-pentene-l),ethylenepropylene random and block copolymers and terpolymers ofethylene-propylene-butene-1 as well as many others.

The polymerizable compounds include those defined wherein R is a cyclic,straight or branched chain alkylene wherein Yrepresents oxygen or sulfuratoms, R is a straight or branched chain alkylene radical having one to10 carbon atoms,

oxygen, sulfur, or

wherein R is H or lower alkyl and R is lower alkyl; and n is an integerof 1 to 2D; a -CHzEO-O(R"0)x wherein R is 1dw'r5iiyiIfi ah iiiie e6511536 and z is an integer ofl to 10;

.i 14 l a -CH O-R j group wherein R is lower alkyl and r is an integerof l to a C, to C 10 bisphenol, the monoglycidyl ether of oxybisphenol,the monoglycidy] ether of thiobisphenol, the monoglycidyl ether ofaminobisphenol and the monoglycidyl ether of a, a-bis(p-hydroxyphenyl)toly lethane; theacrylic and methacrylic esters of 3-oxy-6,7-epoxyheptanol, 3-aza-6,7-epoxyheptanol, or 3-thia-6,7-epoxyhaptanol; the reaction products of one mole of acrylic ormethacrylic acid with one mole of polyphenylenesulfide diglycidyl ether,polyphenyleneamine diglycidyl ether, or polyphenyleneoxide diglycidylether; the reaction products of one mole of acrylic acid or methacrylicacid with one mole of the .polycondensation product of epichlorohydrinwith sulfonyl bis(phenylmercaptan) or sulfonyl bisphenol; the reactionproducts of one mole of acrylic acid or methacrylic acid with one moleof the polycondensation product of epichlorohydrin with a, a-bis(p-,hydroxyphenyl) tolylethane or a, d-bis(p-thiophenyl)- tolylethane; theacrylic and-methacrylic esters of poly (C C alkyleneoxide glycol)monoglycidyl ether; and the acrylic and methacrylic esters of poly[(co-alwherein R is hydrogen or an alkyl radical having one to fourcarbon atoms; 7

R is a straight, branched or cyclic alkylene radical having one to 10carbon atoms with or without pendant glycidoxy groups; a substituted orunsubstituted phenylene group with or without pendant glycidoxy groups;

with or without pendant glycidoxy groups;

a -(IJO-(Cr-G1o a1kylene)-- group with or without pendant glycidoxygroups; or

with or without pendant glycidoxy groups; and

R? is halogen (bromine or chlorinein particular), an alkoxy radicalhaving one to 10 carbon atoms, or an acyloxy radical having one to 10carbon 'atorns.

Preferably, R is absent or a C -C alkylene groupwhile R and R are asdescribed above. 7

Included within the above defined group of compounds are the followingby structure Such compounds are commercially available.

The acrylic esters of diols or triols which may be used I as themodifier in the invention include those-defined by the following formulawherein R" is H. or C -C4 alkyl;

lg mo o s u wherein R is defined above;

wherein R is defined above and R is H 'or The above acrylic. esters areeither commercially available or may be prepared by conventional directesterification techniques involving reaction between acrylic acid ormethacrylic acid and the particular diol or triol. Conventionalacylation techniques may also be used wherein acryloyl chloride ormethacryloyl chloride are substituted for the acids in reacting with thediols or triols. Any diol or triol coming within the scope of thecorresponding portion of the above structural formula may be used forsuch preparation. For example, ethylene glycol, diethylene glycol,triethylene glycol, tetraethylene glycol, propylene glycol, dipropyleneglycol, polypropylene glycols, hexyl ene glycol, 2-methyl-2-ethyl-l,3-propanediol, 2-ethyl-l ,3- hexanediol, l,5-pentanediol, glycerine,1,2,6-hexanetriol, triethanol. amine, diethanol amine, 1,4-butanediol,polyethylene glycol, 1,2,4-hexanetriol, trimethylol ethane, trimethylolpropane, poly(oxypropylene)-poly(oxyethylene') glycols and alkylenetriols, poly(oxypropylene-oxyethylene) glycols and al-.

kylene triols, and the like.

wherein R is H or C -C4 alkyl; and R is A i-Elem -wherein R is H orCH;;.

' As mentioned above the improved "modified polyolefin compositions ofthis invention are derived by reacting the olefin polymer, theethylenically unsaturated compound and the acrylic ester or mixture ofacrylic esters in the presence of an organic peroxide. Normally, suchorganic peroxide is employed in an amount in the range of about 0.01 by5 percent by weight based on the olefin polymer.

tial adverse effect on free radical polymerization reac-. tions, asuitablephysical form is obtained which can be 40 used withsubstantially equal success in the process of the invention. Since thesolvent, for this purpose, 'mer'ely functions as a carrier for the solidorganic peroxide it makes no difference whether or not it becomesvaporized prior to reaching reaction temperature since the peroxide atthat point in the process has already been distributed throughout theingredients.

Some examples of suitable peroxides include di-tbutyl peroxide,t-butylhydroperoxide, methyl ethyl ketone peroxide, t-butyl perbenzoate,t-butyl peracetate, t-butyl peroxypivalate, acetyl peroxide, tbutylperoctoate t-butyl peroxyisobutyrate, decanoyl peroxide, lauroylperoxide, benzoyl peroxide,- 2,5- dimethylhexane-2,S-diperoxybenzoate,cyclohexanone peroxide, cumene hydroperoxide, p-methane hydroperoxide,-di-t-butyl-diperoxyphthalate, cumyl peroxide, caproyl peroxide, and thelike. Of course, there are additional organic peroxides in this groupbut are too numerous to attempt to individually name. In the event it isdesirable to use a solvent some which would be suitable include benzene,mineral spirits, toluene, chlorobenzene, dichlorobenzene, acetone,dimethyl phthalate, t-butyl alcohol, anisole, decalin, xylene and otherswhich possess the required inertness to the reaction. As mentionedpreviously, it is preferred .that the organic peroxide be in a liquidform or capable 50 psi.

or near the temperature at which the particular reaction is carried out.

It is pointed out that oxygen cannot be employed in the process eventhough it is sometimes regarded as a 5 free radical initiator. Oxygen isknown to cause deleterious effects on polymerizable monomers such as theethylenically unsaturated compounds and acrylic esters used in thisinvention (see page 36 of the reprint of Chapters l-lV from MonomericAcrylic Esters by E.

H. Riddle, 1954).

Selection of a particular organic peroxide or mixture of organicperoxides of the type mentioned above may be easily determined based onthe temperature at which the particular reaction is to be carriedout andthe correspondingdecomposition rate of the peroxides as evidenced bytheir respective half-lives. The halflives of peroxides are well knownand may be readily ascertained (see US. Pat. No. 3,293,233 and. En:

cyclopedia ofChemical Technology, Kirk-Othmer, 2nd

Edition, Vol. 14, p. 810-813).

. The manner in which the materials are reacted is not critical. Thus,for example, it may be expeditious to merely admix the materials usingany type of mixing device and, after charging the mixture to a reactor,

heating the mixture to an optimum temperature whereat the organicperoxide decomposes to generate free radicals. The reaction may beconducted with all of the ingredients dissolved in inert solvents orwhile in a molten state. The olefin polymer may be molten or in solidparticulate form while the remaining ingredients are in a liquid ordissolved state.

The temperature is also'not critical for conducting the reaction exceptto the extent that it must not be so high as to cause degradation of theolefin polymer, the

ethylenically unsaturated compound, or' the acrylic esters. As mentionedabove, the temperatures employed go hand-in-hand with the particularperoxide selected. For example, if it is desired to conduct the reactionat a low temperature one would most likely select a peroxide having alow temperature 10-hr. halflife, e.g. acetyl peroxide for use at aboutroom temperature.

The pressure at which the reaction is conducted is not critical and, ingeneral, good results can be obtained at pressures in the range ofatmospheric up to about 1000 psi. For practical reasons it is convenientto operate at pressures of atmospheric up to about 200 55 system effortshould be madeto prevent introduction of additional oxygen over andabove what may be initially present. Preferably, the reactor is purgedwith an inert gas prior to conducting the reaction.

In conducting the reaction using a solid form of polyolefin it isdesirable to substantially completely decompose the organic peroxidebefore recovering the product as the presence of any residual peroxide,even in small quantities, may adversely affect the resulting compositionin subsequent compounding, molding or extruding operations. Of course,if one can tolerate certain of the adverse effects then the extent ofdecomposition of the peroxide may be somewhat incomplete. The reactionproduct, that is the resulting composidants, slip agents, anti-staticagents, mold release agents, flame retardants and the like.

The following examples will serve to further illustrate the invention.

EXAMPLE 1 A mixture comprising 100 parts by weight polypropyleneparticles (average size in the range of 0.01 mm to 4 mm), 0.5 part byweight glycidyl acrylate, 0.5 part by weight t-butyl peracetate (75percent solution in benzene) and 1.55 parts by weight ethylene glycoldimethacrylate were mixed in a Waring blender and charged to a reactorwith a paddle stirrer. The dry-.

appearing mixture was stirred to distributethe materials while firstpurging the system with argon and then heating to about 125 C underautogenous pressure.

The mixture was maintained at about 125 C for about 4 hours whilecontinuing the stirring and then cooled and subjected to vacuum toremove any volatiles present. The resulting composition was recovereddirectly from the reactor in a particulate form.

Using the same procedure outlined in the previous paragraph a secondcomposition was prepared except that 1.76 parts by weight 1,3-buty1enedimethacrylate were substituted for the ethylene glycol dimethacrylate.The product again was recovered in a particulate form.

For comparison, a third composition was prepared using the sameprocedure except that no ethylene glycol dimethacrylate or 1,3-butylenedimethacrylate was employed. The product composition was recovered in'aparticulate form.

Each of the above compositions was tested for melt flow (230 C) inaccordance with ASTM D-1238 and then blended with 20 weight percentchopped glass fibers ('/4 inch, OCF 885) for testing for flexuralstrength and flexuralmodulus properties in accordance with ASTMD-790-66. The results of these evaluations are indicated in thefollowing table.

1,3-buty1ene dimethacrylate all samples prepared using 0.5 part byweight peroxide trimethacrylate, or (5) no additional ingredient. The

l .8 EXAMPLE 2 A similar series of compositions were prepared as inExample 1 for comparisonexcept that the mixtures being reacted comprisedparts by .weight polypropylene, 0.5 part by weight glycidyl acrylate,0.25 part by weight t-butyl peracetate and (1) 0.78 part byweightethylene glycol dimethacrylate, or (2) 1.55 part'by weight ethyleneglycol dimethacrylate, or (3) 0.5 part by weight trimethylol propanetrimethacrylate, 1.0 part by weight trimethylol propane compositionswere tested as in Example 1 and the results are indicated in thefollowing table.

TABLE 2 EGDM TMPTM". Flexural Flexural Sample (Parts by (Parts by MeltStrength Modulus(psi) No. Weight Weight) Flow (psi) (X10") 1A 0.78 2016,400 4.7 18 0.78 18 15,800 4.7 2 1.55 13 15,200 4.4 3A 0.5 15 15,7005.4 38 0.5 19 16,300 5.6 4A 1.0 4 14,500 5.1 4H 1.0 10 14,600 5.0 5A 3812,000 3.8 58 38 14,300 4.6

ethylene glycol dimethacrylate trimethylol propane trimethacrylate allsamples prepared using 0.25 part by weight peroxide EXAMPLE 3 Anotherseries of compositions were prepared as in Example 1 for comparisonexcept that the mixtures being reacted comprised 100 parts by weightpolypropylene, 1.0 part by weight glycidyl acrylate, 0.5 part by weightt-butyl peracetate and (l) 1.0 part by weight trimethylol propanetrimethacrylate, or (2) no additional ingredient. The compositions weretested as in Example 1 and the results are indicated in the followingtable.

TABLE3 TMPTM' Flexural Flexural Sample (Parts by Melt StrengthModulus(psi) No. Weight) Flow (psi) (X10) 1A 1.0 22 14,300. 4.7 18 1.024 15,200 5.1 2A 62 14,600 '4.3 25 54 15,100 4.4 2C 48 14,100 4.5

trimethylol propane trimethacrylate all samples prepared using 0.5 partby weight peroxide EXAMPLE 4 Another series of compositions wereprepared as in Example 1 for comparison except that the mixtures beingreacted comprised 100 parts by weight polypropylene, 0.2 part by weight'y-methacryloxypropyl trimethoxy silane, 0.5 part by weight t-butylperacetate and (1) 0.78 part by weight ethylene glycol dimethacrylate,or (2) no additional ingredient. The compositions were tested as inExample 1 and the results are indicated in the following table.

EXAMPLE 5 g A series of compositions were prepared as in Example 1except that in each case the ingredients were charged to a 1 liter flaskwhich was then partially immersed in a heated oil bath and continuouslyrotated.

The oil bath was heated sufficiently to maintain the flask at atemperature of about 125 C. About 75 hour was allowed for warm-up of theflask and the reaction was then allowed to proceed for about four hours.Each composition was recovered in a particulate form. The compositionsprepared comprised 100 parts by weight polypropylene, 0.25 part byweight glycidyl acrylate, 0.10 part by weight t-butyl peracetate and (l0.125

1 part by weight ethylene glycol dimethacrylate, or (2) 0.25 part byweight ethylene glycol dimethacrylate, or

(3) 0.5 part by weight ethylene glycol dimethacrylate,-

or (4) no additional ingredient. The compositions were testedas inExample 1 and the results are indicated in the following table.

EXAMPLE 6 Using the same procedure as in Example 5a series ofcompositions were prepared comprising 100 parts by weight polypropylene,0.2 parts by weight 'y-methacyloxypropyl trimethoxy silane, 0.25 part byweight of S-butyl peracetate and (1) 0.2 part by weight ethylene glycoldimethacrylate, or (2) no additional ingredient. The compositions weretested as in Example 1 and the results are indicated in the followingtable.

TABLE 6" EGDM' Flexural Flexural Sample (Parts by Melt StrengthModulus(psi) No. Weight) Flow (psi) (X1 0") ethylene glycoldimethacrylate all samples prepared using 0.25 part by weight peroxideFrom the data of Tables 1 6 it is theorized that the quantity ofperoxide used in the reaction may have an effect on the melt flow of thecompositions, the greater the quantity of peroxide the higher the meltflow. However, in each table it is also apparent that in a series ofspecific reactions employing a specific quantity of peroxide the use ofthe modifiers results in compositions of reduced melt flow and generallybetter physical properties. I

v.Thus having described the invention in detail it will be understood bythose skilled in the art that certain variations and modifications maybe made without departing from the spirit and scope of the invention asdescribed herein or in the appended claims.

We claim:

1. A reaction product of A. at least one olefin polymer derived fromalphaolefin monomers having two to 10 carbon atoms,

B. at least one polymerizable compound defined by wherein R is a cyclic,straight or branched chain alkylene group having one to 20 carbon atoms,

wherein R is H or lower alkyl and R is lower alkyl;

R-X-R3 group wherein each R is a straight or branched chain loweralkylene, X is an amino group or an oxygen or sulfur atom, and p is aninteger of 1 to 20;

' wherein R" is lower alkyl, x is an integer of l to and 11 wherein 'Yrepresents oxygen or'sulfur atoms, R is a straight or branched chainalkylene radical having one to l0carbon atoms, 1

wherein R" is H or lower alkyl and R is lower alkyl; and 'n is aninteger of l to swan z isan integer ofl to 10;

a -CH,[ o-nw j group wherein R is lower alkyl and Tis an integer of l to100; j

aCH OCH,OCH -CH ,group wherein sis an integer ofl to 100; and R is H orCH and C.'at least one modifier defined by the formula wherein R" is Hor (if-C alkyl;

wherein R is defined above and R is H or wherein R is defined above; Rfor each unit is H or -CH;;; and R is wherein R is H or --CH;;.

in the presence of an organic peroxide whereinthe polymerizable compoundis present in the range of 0.0! to 10 percent by weight based on theolefin polymer and the modifier is present in the range of 0.01 to 10'percent based on the olefin polymer.

2. A reaction product according to claim 1 wherein the olefin polymer ispolypropylene, polyethylene, or a copolymer of ethylene and propylene. I

3. A reaction product according to claim 1 wherein the polymerizablecompound is glycidyl acrylate;

glycidyl methacrylate; the acrylic and methacrylic esters of themonoglycidyl ether of sulfonyl bis-phenol, the monoglycidyl ether of aC, to C alkylene bisphenol, the monoglycidyl ether of oxybisphenol, themonoglycidyl ether of thiobisphenol, the monoglycidyl ether ofaminobisphenol and the monoglycidyl ether of a, a-bis(p-hydroxyphenyl)tolylethane; the acrylic and methacrylic esters of3-oxy-6,7-epoxyheptanol, 3-aza- 6,7-epoxyheptanol and3-thia6,7-epoxyheptanol; the

reaction products of one mole of acrylic ormethacrylic acid with onemole of polyphenylenesulfide diglycidyl ether, polyphenyleneaminediglycidyl ether, or polyphenyleneoxide diglycidyl ether; the reaction.productsof one mole of acrylic acid or meth'acrylic 1 acidwith onemoleof the polycondensation product of epichlorohydrin with sulfonylbis(phenylmercaptan) or sulfonyl bisphenol; the reaction products of onemole I of acrylic acid or methacrylic acid with one mole of thepoly-condensation product of epichlorohydrin with a,abis(p-hydroxy-phenyl) tolylethane or 0t, a-bis(pthiophenyl)tolylethane; the acrylic and methacrylic esters of poly (C Calkylene-oxide glycol) monoglycidyl ether; and the acrylic andmethacrylic esters of poly[(co-alkylene-phenylene-oxide) glycol]monoglycidyl ether.

4.. The reaction product according to claim 1 wherein the polymerizablecompound is glycidyl acrylate or glycidyl methacrylate; and the modifieris ethylene glycol diacrylate, ethylene glycol dimethacrylate,trimethylol triacrylate, trimethylol trimethacrylate, 1,3-butylenediacrylate, or 1,3-butylene dimethacrylate.

5.-The reaction product according to claim 1 containing 5 to percent byweight reinforcing filamentary material;

6. A metallic article coated with the reaction product of claim 1. 7. Ina process for producing a polymer composition wherein an olefin polymerderived from alpha-olefm monomershaving two to l0 carbon atoms and 0.01to 10 percent by weight based on the olefin polymer of a polymerizablecompound defined by the formula wherein R is a cyclic, straight orbranched chain alkylene group having 1 to 20 carbon atoms;

wherein R is a straight or branched chain alkylene 1 radical having oneto 10 carbon atoms, oxygen, sulfur, amino,

wherein R is H or lower allcyl and Ris lower alkyl; wherein s is aninteger of l to 100; and R is H or CH,,

or are reacted in the presence of an organic peroxide, a 1? g p theimprovement therein of reducing the melt flow of the polymer compositionby including with the inwherein each R is a straight or branched chainlower gredients being reacted 0.01% to 10% by weight based alkylene, Xis an amino group or an oxygen or sulfur on the olefin polymer of amodifier defined by the foratom, and P is an integer of l to 20; mulawherein Y represents oxygen or sulfur atoms, R" is a straight orbranched chain alkylene radical having 1 to R"( 3-0- -CH1 -CR"H-0 R" 10carbon atoms, m H0 0 R"&0-CH -CR"HO Ru g /o-m.

' oxygen, sulfur, or Y 1 r -CR192,- E p /o-io I I iwherein R is H or C-C alkyl;

- r r CR 0CR R12 i 2 /0-40 iwherein R is defined above;

wherein R is H or lower alkyl and R is lower alkyl; 3 19,. i9 and n isan integer of l to 20; I 1

.l wherein R is defined above and R is H or a -orn-o- 0-(R -o x f J:

L -CH:0R" or [R H2)o-i-0-R group r I wherein R is defined above; R" foreach unit is H 5 -or CH and R is wherein R IS lower alkyl, x is aninteger of 1 to 10 and z is an integer of 10 to 10; E E

=CHa a CH2 O R group wherein R is H or -CH 8. A process according toclaim 7'wherein the reacwherein R is lower alkyl and r is an integer oflto 40 00; tion is conducted in the absence of oxygen.

2 2 z- 2 1 g p a:

Z22 3? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.34,99,135 Dated October 17, 1972 Inventor(s) Al begt Schfgge et a1 It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Home 1, line 65 the portion of the formula readin R2 a should read r R2Column 11, line 29 the formula: I -cH [0-cH '-0-cH :H should read'-CH2[0-CH20-CH2-CH2]S Colunm 11, line 42 'the formula: I

19 4 l9 (CR 1 i should reed (CB 4 Column 13, line v37 "10 he 10" should,be changed to --1 to 10-- Coluinn 14, line 18 before "R is" insert-whe'rein each R is H or C -C alkyl; I

Signed and sealed this 22nd day of January 1971+.

(SEAL) Attest:

EDWARD M. FLETCBERQJR. RENE D. TEGTL [EYER I Attesting Officer 1 ActingCommissioner of Pate:

2. A reaction product according to claim 1 wherein the olefin polymer ispolypropylene, polyethylene, or a copolymer of ethylene and propylene.3. A reaction product according to claim 1 wherein the polymerizablecompound is glycidyl acrylate; glycidyl methacrylate; the acrylic andmethacrylic esters of the monoglycidyl ether of sulfonyl bis-phenol, themonoglycidyl ether of a C1 to C10 alkylene bisphenol, the monoglycidylether of oxybisphenol, the monoglycidyl ether of thiobisphenol, themonoglycidyl ether of aminobisphenol and the monoglycidyl ether of Alpha, Alpha -bis(p-hydroxyphenyl) tolylethane; the acrylic and methacrylicesters of 3-oxy-6,7-epoxyheptanol, 3-aza-6,7-epoxyheptanol and3-thia-6,7-epoxyheptanol; the reaction products of one mole of acrylicor methacrylic acid with one mole of polyphenylenesulfide diglycidylether, polyphenyleneamine diglycidyl ether, or polyphenyleneoxidediglycidyl ether; the reaction products of one mole of acrylic acid ormethacrylic acid with one mole of the polycondensation product ofepichlorohydrin with sulfonyl bis(phenylmercaptan) or sulfonylbisphenol; the reaction products of one mole of acrylic acid ormethacrylic acid with one mole of the poly-condensation product ofepichlorohydrin with Alpha , Alpha -bis(p-hydroxy-phenyl) tolylethane orAlpha , Alpha -bis(p-thiophenyl) tolylethane; the acrylic andmethacrylic esters of poly (C1-C4 alkylene-oxide glycol) monoglycidylether; and the acrylic and methacrylic esters of poly((co-alkylene-phenylene-oxide) glycol) monoglycidyl ether.
 4. Thereaction product according to claim 1 wherein the polymerizable compoundis glycidyl acrylate or glycidyl methacrylate; and the modifier isethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethyloltriacrylate, trimethylol trimethacrylate, 1,3-butylene diacrylate, or1,3-butylene dimethacrylate.
 5. The reaction product according to claim1 containing 5 to 90 percent by weight reinforcing filamentary material.6. A metallic article coated with the reaction product of claim
 7. In aprocess for producing a polymer composition wherein an olefin polymerderived from alpha-olefin monomers having two to 10 carbon atoms and0.01 to 10 percent by weight based on the olefin polymer of apolymerizable compound defined by the formula wherein R1 is a cyclic,straight or branched chain alkylene group having 1 to 20 carbon atoms;wherein R6 is a straight or branched chain alkylene radical having oneto 10 carbon atoms, oxygen, sulfur, amino, wherein R7 is H or loweralkyl and R8 is lower alkyl; a ( R9-X-R9 )P group wherein each R9 is astraight or branched chain lower alkylene, X is an amino group or anoxygen or sulfur atom, and P is an integer of 1 to 20; wherein Yrepresents oxygen or sulfur atoms, R10 is a straight or branched chainalkylene radical having 1 to 10 carbon atoms, wherein R11 is H or loweralkyl and R12 is lower alkyl; and n is an integer of 1 to 20; whereinR13 is lower alkyl, x is an integer of 1 to 10 and z is an integer of 1to 10; a -CH2 ( O-R14 )r group wherein R14 is lower alkyl and r is aninteger of 1 to 100; a -CH2 ( O-CH2-O-CH2-CH2 ) s group wherein s is aninteger of 1 to 100; and R2 is H or CH3, or are reacted in the presenceof an organic peroxide, the improvement therein of reducing the meltflow of the polymer composition by including with the ingredients beingreacted 0.01% to 10% by weight based on the olefin polymer of a modifierdefined by the formula
 8. A process according to claim 7 wherein thereaction is conducted in the absence of oxygen.